Substituted 3-aminopyrazoles

ABSTRACT

New and valuable pyrazole derivatives having a good herbicidal action, herbicides containing these compounds as active ingredients, and processes for controlling the growth of unwanted plants with these compounds.

This is a continuation of application Ser. No. 181,145, filed Aug. 25, 1980, now abandoned, which is a division of application Ser. No. 951,566, filed Oct. 16, 1978, now U.S. Pat. No. 4,260,775.

The present invention relates to new and valuable pyrazole derivatives having a good herbicidal action, herbicides containing these compounds as active ingredients, and processes for controlling the growth of unwanted plants with these compounds.

It is known that substituted pyrazoles or pyrazolium salts, e.g. 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate, can be used as herbicides (German Laid-Open Applications DOS Nos. 2,513,750 and 2,260,485). It is also known that 2-(1-methyl-n-propyl)-4,6-dinitrophenyl acetate (German No. 1,088,575) or 3-isopropyl-2,1,3-benzothiadiazin-4-on-2,2-dioxide (German No. 1,542,836) may be used as herbicides.

We have now found that substituted pyrazoles of formula (1) ##STR1## where R¹ denotes hydrogen or lower, unsubstituted or substituted alkyl or acyl, or cyano, alkoxycarbonyl, alkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminocarbonyl, dialkylaminothiocarbonyl, unsubstituted or substituted benzoyl, alkylsulfonyl, unsubstituted or substituted phenylsulfonyl, unsubstituted or substituted aryloxycarbonyl, arylamino-(thio)-carbonyl or alkylaminosulfonyl,

R² denotes hydrogen or lower unsubstituted or alkoxy-substituted alkyl, or acyl,

R³ denotes unsubstituted alkyl or alkyl substituted by alkoxy, alkylthio, alkoxycarbonyl, cyano, halogen, aryl or a heterocyclic radical, or R³ denotes cycloalkyl, bicycloalkyl, alkenyl, cycloalkenyl, or unsubstituted phenyl or phenyl bearing one or more alkyl, alkoxy, alkylthio, nitro, haloalkyl, haloalkoxy, cyano, halogen, carbalkoxy or hydroxy substituents, or unsubstituted pyridyl or pyridyl substituted in the same way, or R² and R³ together denote unsubstituted or substituted polymethylene which may contain hetero atoms

R⁴ denotes halogen, cyano or the radicals ##STR2## R⁶ denoting unsubstituted or halogen-, alkoxy- or alkylthio-substituted methoxy, propoxy or isopropoxy, or lower unsubstituted or halogen-, alkoxy- or alkylthio-substituted alkyl, or alkylthio, amino, alkylamino or dialkylamino, X denotes oxygen or sulfur, and Me⁺ denotes an equivalent of a cation of the metals Li, Na, K, Mg, Ca, Ba, Al, Fe, Co, Ni, Mn, Cu and Zn, and R⁵ denotes hydrogen or unsubstituted or halogen-, alkylthio-, alkoxy- or alkoxycarbonyl-substituted alkyl, or halogen, alkoxy, hydroxy, alkoxycarbonyl or unsubstituted phenyl or phenyl bearing one or more alkyl, alkoxy, alkylthio, nitro, haloalkyl, cyano, halogen, carbalkoxy or hydroxy substituents, and furthermore, R⁶ denotes ethoxy, in which case R¹ does not simultaneously denote hydrogen, R⁵ does not simultaneously denote methyl, R² does not simultaneously denote hydrogen, and R³ does not simultaneously denote methyl, ethyl or unsubstituted phenyl or phenyl bearing methyl, chlorine or trifluoromethyl in 2- and/or 3-position or R¹ does not simultaneously denote hydrogen, R⁵ does not simultaneously denote methyl, R² does not simultaneously denote methyl and R³ does not simultaneously denote methyl, and R⁶ also denotes hydroxy, in which case R¹ does not simultaneously denote hydrogen, R² does not simultaneously denote hydrogen, R³ does not simultaneously denote unsubstituted phenyl or phenyl bearing methyl or trifluoromethyl in 2- and/or 3-position and R⁵ does not simultaneously denote methyl, and the salts and metal complex compounds thereof, exhibit a good herbicidal action and a selective herbicidal action as regards crop plants and may be used as desiccants in various plants.

The new substituted 3-aminopyrazoles may be in the form of their salts with conventional strong inorganic or organic acids, such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, tetrafluoboric acid, fluosulfonic acid, formic acid, a halogenated carboxylic acid, e.g. trichloroacetic acid, an alkanesulfonic acid, e.g. methanesulfonic acid, a halogenated alkanesulfonic acid, e.g. trifluomethanesulfonic acid, perfluohexanesulfonic acid, and an arylsulfonic acid, e.g. dodecylbenzenesulfonic acid.

On account of the tautomeric structure, two isomers occur in the starting materials of the new substituted 3-aminopyrazoles: ##STR3##

The isomer ratio is determined substantially by the various substituents. Therefore any formula or name may be understood to be either of the two isomers.

The new substituted 3-aminopyrazoles may be in the form of their metal complex compounds with transition metals, for example copper, iron, zinc, manganese, cobalt and nickel.

R¹ may for example denote the following: hydrogen, methyl, ethyl, n-propyl, isopropyl, isobutyl, sec-butyl and tert-butyl, formyl, acetyl, propionyl, chloroacetyl, bromoacetyl, trichloroacetyl, trifluoroacetyl, 2,4-dichlorophenoxyacetyl, (2,4-dichlorophenoxy)-propionyl, cyano, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, phenoxycarbonyl, methylaminocarbonyl, isopropylaminocarbonyl, benzoyl, 2',4'-dichlorobenzoyl, methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, phenylsulfonyl, 4-methylphenylsulfonyl, methylaminosulfonyl, isopropylaminosulfonyl, 3-chlorophenoxycarbonyl, 3,4-dichlorophenoxycarbonyl, 3-(methoxycarbonylamino)-phenoxycarbonyl, 2-methyl-4-chlorophenoxycarbonyl, methylaminothiocarbonyl, dimethylamino-(thio)-carbonyl, phenylamino-(thio)-carbonyl, and 3,4-dichlorophenylamino-(thio)-carbonyl.

R² may for example denote the following: hydrogen, methyl, ethyl, n-propyl; isopropyl, 1-methoxy-2-propyl, formyl, acetyl and chloroacetyl.

R³ may for example denote the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 3-methyl-2-butyl, pentyl-2, pentyl-3, hexyl-2, hexyl-3, 2-ethyl-pentyl-3, 2,4-dimethyl-pentyl-3, 2-ethylhexyl, dodecyl, 1-methoxy-2-propyl, 1-fluoro-2-propyl, 1-chloro-2-propyl, 1,1,1-trifluoro-2-propyl, 1-cyano-2-propyl, 1-methoxycarbonyl-2-propyl, 2-(methoxycarbonyl)-2-propyl, benzyl, α-phenylethyl, β-phenylethyl, 2-(pyrazolyl-1)-ethyl, 2-(imidazolyl-1)-ethyl, 2-(1',2',4'-triazolyl)-ethyl, allyl, buten-1-yl-3, butyn-1-yl-3, 3-methyl-buten-1-yl-3, 3-methyl-butyn-1-yl-3, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-methylcyclohexyl, 2-methoxycyclohexyl, 3-trifluoromethylcyclohexyl, 1,1-dimethoxypropyl-2, phenyl, 2-methylphenyl, 2-fluorophenyl, 3-chloro-4-fluorophenyl, 2,4-dichlorophenyl, 3,5-dichlorophenyl, 3-methoxyphenyl, 2,5-dimethoxyphenyl, 2-cyanophenyl, 2-nitrophenyl, 3-nitrophenyl, 2-methylthiophenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 2-methoxycarbonylphenyl, 3-methoxycarbonylphenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, pyridyl-2, pyridyl-3, pyridyl-4, 3-fluorophenyl, 2-chlorophenyl, 3,4-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,3-dichlorophenyl, 2,5-dichlorophenyl, 2-methyl-3-chlorophenyl, 2-methyl-5-chlorophenyl, 2-methoxy-5-chlorophenyl, 3-tetrafluoroethoxyphenyl, 2-chloro-5-trifluoromethylphenyl, and 2-methoxy-5-methylphenyl.

R⁴ may for example denote the following: chloro, bromo, cyano, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, methoxythiocarbonyl, thiomethylcarbonyl, methylthiocarbonyl, acetyl, chloroacetyl, dichloroacetyl, trichloroacetyl, trifluoroacetyl, methoxyacetyl, amino, methylamino, dimethylamino, carboxyl, Na carboxylate, magnesium carboxylate, and manganese carboxylate.

R⁵ may for example denote the following: hydrogen, methyl, isopropyl, tert-butyl, chloromethyl, methoxymethyl, cyanomethyl, methoxycarbonylmethyl, chloro, bromo, cyano, methoxy, isopropoxy, hydroxy, phenyl, 2-chlorophenyl, 2-methylphenyl, 3-methoxyphenyl, 3-methylthiophenyl, 4-nitrophenyl, 3-trifluoromethylphenyl, 2,4-dichlorophenyl, 3-cyanophenyl, 2-methoxycarbonylphenyl, and 2-hydroxyphenyl.

If R² and R³ together form polymethylene, the latter may contain hetero atoms, e.g. nitrogen, oxygen and sulfur. Together with the nitrogen atom in 3-position of the pyrazole, the following rings are formed for example: ##STR4## tetramethyleneimino, pentamethylenimino, hexamethylenimino, morpholino, thiomorpholino, and piperazino.

The ring formed together with R² and R³ may contain additional substituents such as alkyl, alkoxy, halogen and cyano.

Processes for the production of the new pyrazole derivatives are described for example in Chem. Ber. 98, 259 (1965).

Another method consists in condensing aldehydes, ketones or α-ketocarboxylic acid derivatives with 3-amino-4-alkoxycarbonyl pyrazoles which may be unsubstituted or substituted in 5-position, and subsequently hydrogenating the Schiff bases thus obtained.

The pyrazoles acylated in 1- or 2-position are obtained by subsequent acylation of the 3-aminopyrazole derivatives by conventional methods.

The salts of the new pyrazoles are prepared by reacting the pyrazoles with the acids in a solvent. The metal complex compounds of the new pyrazoles are prepared by reacting the pyrazoles with the metal salts in a solvent.

The processes selected for preparing the new pyrazoles are illustrated by the following Examples.

EXAMPLE 1 3-anilino-4-isopropoxycarbonyl-5-methylpyrazole

35.7 g of isopropyl 2-chloroacetate is added to a suspension of 33.5 g of 4-phenylthiosemicarbazide in 150 ml of tetrahydrofuran. After the mixture has been stirred for 30 minutes it is boiled for a further 30 minutes and then allowed to cool. The precipitated solid is isolated by suction filtering, washed with acetone and the residue is heated in a water/acetone mixture (1:1). After the separated sulfur has been poured off, the whole is allowed to cool and is neutralized with aqueous NaHCO₃, solution and the precipated solid is isolated; m.p. 138°-139° C. (from toluene).

EXAMPLE 2 2-isobutylamino-4-methoxycarbonyl-5-methylpyrazole

15.1 g of methyl 2-chloroacetate is added to a suspension of 14.7 g of 4-isobutylthiosemicarbazide in 150 ml of tetrahydrofuran. The mixture is stirred for 30 minutes and then boiled. After stirring for a further hour at 65° C., the mixture is cooled, the precipitated solid is isolated and washed with acetone. The residue is dissolved hot in water, filtered off from the precipitated sulfur and, after cooling, aqueous ammonia solution is added. After suction filtering and drying the product, 3-isobutylamino-4-methoxycarbonyl-5-methylpyrazole is isolated; m.p. 100°-103° C.

EXAMPLE 3 3-piperidino-4-methoxycarbonyl-5-methylpyrazole

4,4-pentamethylenethiosemicarbazide (m.p. 98°-99° C.) was prepared by the method disclosed in J. pr. Ch. (2) 159, 189 (1941). 32 g of 4,4-pentamethylenethiosemicarbazide is added to 100 ml of tetrahydrofuran (THF) and the whole is mixed with 31 g of methyl 2-chloroacetate. After stirring for one hour at room temperature, the solid formed is suction filtered, washed with acetone and dissolved in H₂ O, and aqueous ammonia solution is added until the alkaline reaction (pH 8). The oil which separates is separated from the sulfur by extraction with CH₂ Cl₂. After being concentrated it is recrystallized from acetone; m.p. 101°-102° C.

EXAMPLE 4 3-anilino-4-acetyl-5-methylpyrazole

50 g of 4-phenylthiosemicarbazide is suspended in 300 ml of tetrahydrofuran and 0.5 ml of concentrated HCl is added. Then 40.4 g of 3-chloroacetyl acetone is allowed to run in all at once and the whole is cooled with an ice-bath. After 12 hours' stirring, the precipitate formed is suction filtered, washed with acetone and then boiled in a water/acetone mixture (1:1). This hot solution is filtered off from the sulfur and neutralized with aqueous ammonia solution. The product is then suction filtered and recrystallized from acetone; m.p. 246°-247° C.

EXAMPLE 5 3-benzylamino-4-ethoxycarbonylpyrazole

21.2 g of benzaldehyde is added to a suspension of 25 g of 3-amino-4-ethoxycarbonylpyrazole in 200 ml of toluene. The whole is boiled while separating water. In 3 hours a total of 5 ml of water collects. After the toluene has been evaporated, 50 ml of methanol and 50 ml of THF are added and, under cooling, 23 g of NaBH₄ is added at 0°-5° C. After 4 hours' at room temperature, the solvent mixture is drawn off; then 200 ml of ice water is added the whole is extracted three times with 150 ml of methylene chloride each time and the extract is dried over Na₂ SO₄. After concentration, an oil remains that is recrystallized from ligroin/toluene; m.p. 99°-100° C.

EXAMPLE 6 2,5-dimethyl-3-anilino-4-methoxycarbonylpyrazole

36.2 g of 2-methyl-4-phenylthiosemicarbazide is dissolved in 200 ml of methanol and 30.2 g of methyl 2-chloroacetate is added. After one hour's stirring, 10 ml of concentrated HCl is added, and the whole is then boiled. After the sulfur has separated, the mixture is allowed to cool, the sulfur is removed and the residue is evaporated.

The crystalline residue is neutralized with aqueous ammonia solution, separated and, after drying, recrystallized from hexane; m.p. 83°-86° C.

The compound 2,5-dimethyl-3-cyclohexylamino-4-methoxycarbonylpyrazole may be prepared analogously; b.p. (0.5 mm Hg) 113°-117° C.

EXAMPLE 7 2-phenyl-3-anilino-4-carboxymethyl-5-methylpyrazole

The same method was used as in Example 6 except that 2,4-diphenylthiosemicarbazide was used and THF as solvent; m.p. 111°-113° C.

The following tables contain some of the compounds that have been obtained according to a process of Examples 1-7 .

                                      TABLE 1                                      __________________________________________________________________________      ##STR5##                                                                      __________________________________________________________________________     No. R.sup.2                                                                              R.sup.3  R.sup.5 R.sup.6                                                                             m.p. (°C.)                              __________________________________________________________________________     1   H     phenyl   tert-butyl                                                                             CC.sub.2 H.sub.5                                                                    108-110                                        2   H     phenyl   phenyl  "    143-145                                        3   H     phenyl   4-nitrophenyl                                                                          "    154                                            4   H     sec.-butyl                                                                              methyl  "                                                   5   H     tert.-butyl                                                                             methyl  "                                                   6   H     phenyl   hydrogen                                                                               "                                                   7   H     methyl   phenyl  "                                                   8   H     methyl   4-chlorophenyl                                                                         "                                                   9   H     methyl   tert.-butyl                                                                            "                                                   10  H     phenyl   hydrogen                                                                               OCH.sub.3                                                                           123-124                                        11  H     cyclohexyl                                                                              hydrogen                                                                               "                                                   12  H     tert.-butyl                                                                             hydrogen                                                                               "                                                   13  H     sec.-butyl                                                                              hydrogen                                                                               "                                                   14  H     phenyl   methyl  "    183-185                                        15  H     2-methylphenyl                                                                          methyl  "    175-177                                        16  H     3-methylphenyl                                                                          methyl  "    188-190                                        17  H     4-methylphenyl                                                                          methyl  "    178-179                                        18  H     2-ethylphenyl                                                                           methyl  "    166-167                                        19  H     2,6-dimethyl-                                                                           methyl  "    190                                                      phenyl                                                               20  H     2-methoxy-                                                                              methyl  "    194                                                      phenyl                                                               21  H     3-methoxy-                                                                              methyl  "    173                                                      phenyl                                                               22  H     4-methoxy-                                                                              methyl  "    168-170                                                  phenyl                                                               23  H     2-hydroxy-                                                                              methyl  "                                                             phenyl                                                               24  H     3-hydroxy-                                                                              methyl  "                                                             phenyl                                                               25  H     4-hydroxy-                                                                              methyl  "                                                             phenyl                                                               26  H     2-chlorophenyl                                                                          methyl  "                                                   27  H     3-chlorophenyl                                                                          methyl  "    206-207                                        28  H     4-chlorophenyl                                                                          methyl  "    201-202                                        29  H     2-fluorophenyl                                                                          methyl  "    190-191                                        30  H     3-fluorophenyl                                                                          methyl  "    182-184                                        31  H     4-fluorophenyl                                                                          methyl  "    186-187                                        32  H     2-trifluoro-                                                                            methyl  "    182-183                                                  methylphenyl                                                         33  H     3-trifluoro-                                                                            methyl  "    198                                                      methylphenyl                                                         34  H     2,5-dimethyl-                                                                           methyl  "    233-235                                                  phenyl                                                               35  H     3,5-dimethyl-                                                                           methyl  "    190-193                                                  phenyl                                                               36  H     2,4-dichloro-                                                                           methyl  "    207-210                                                  phenyl                                                               37  H     3,4-dichloro-                                                                           methyl  "    234-236                                                  phenyl                                                               38  H     2,5-dichloro-                                                                           methyl  "    251-253                                                  phenyl                                                               39  H     3,5-dichloro-                                                                           methyl  "                                                             phenyl                                                               40  H     3-chloro-4-                                                                             methyl  "    212                                                      fluorophenyl                                                         41  H     3,4-difluoro-                                                                           methyl  "    204                                                      phenyl                                                               42  H     2-methyl-3-                                                                             methyl  "    224-226                                                  chlorophenyl                                                         43  H     2-methyl-4-                                                                             methyl  "    205-206                                                  chlorophenyl                                                         44  H     2-methyl-5-                                                                             methyl  "    more than                                                chlorophenyl          240                                            45  H     2-nitrophenyl                                                                           methyl  "                                                   46  H     3-cyanophenyl                                                                           methyl  "                                                   47  H     2-hydroxymethyl-                                                                        methyl  "                                                             phenyl                                                               48  H     2-methylthio-                                                                           methyl  "                                                             phenyl                                                               49  H     2-methoxycar-                                                                           methyl  "                                                             bonylphenyl                                                          50  H     2-azaphenyl                                                                             methyl  "                                                   51  H     3-azaphenyl                                                                             methyl  "                                                   52  H     4-azaphenyl                                                                             methyl  "                                                   53  H     2-methyl-3-aza-                                                                         methyl  "                                                             phenyl                                                               54  H     2-methyl-6-aza-                                                                         methyl  "                                                             phenyl                                                               55  H     methyl   methyl  "    155-157                                        56  H     ethyl    methyl  "    143-144                                        57  H     n-propyl methyl                                                      58  H     allyl    methyl  "    128-130                                        59  H     isopropyl                                                                               methyl  "    100-103                                        60  H     2-methylpropen-                                                                         methyl  "                                                             1-yl-3                                                               61  H     3-methylpropen-                                                                         methyl  "                                                             1-yl-3                                                               62  H     propargyl                                                                               methyl  "                                                   63  H     3-methylpropyn-                                                                         methyl  "                                                             1-yl-3                                                               64  H     3,3-dimethyl-                                                                           methyl  "                                                             propyn-1-yl-3                                                        65  H     3,3-dimethyl-                                                                           methyl  "                                                             propen-1-yl-3                                                        66  H     n-butyl  methyl  "    117-118                                        67  H     iso-butyl                                                                               methyl  "    100-103                                        68  H     sec-butyl                                                                               methyl  "    81-83                                          69  H     tert-butyl                                                                              methyl  "    115                                            70  H     pentyl-2 methyl  "    oil                                            71  H     pentyl-3 methyl  "    81-82                                          72  H     1-methoxy-                                                                              methyl  "    n.sub.D.sup.21 = 1,5122                                  propyl-2                                                             73  H     1,1-dimethyoxy-                                                                         methyl  "                                                             propyl-2                                                             74  H     1-methoxycar-                                                                           methyl  "                                                             bonyl-propyl-2                                                       75  H     1-ethoxycar-                                                                            methyl  "                                                             bonyl-propyl-2                                                       76  H     1-cyano- methyl  "                                                             propyl-2                                                             77  H     1-methoxy-                                                                              methyl  "    oil                                                      butyl-2                                                              78  H     3-methoxy-                                                                              methyl  "    107-108                                                  propyl-1                                                             79  H     1,3-dimethoxy-                                                                          methyl  "                                                             propyl-2                                                             80  H     cyclopentyl                                                                             methyl  "    83-85                                          81  H     2-methylcyclo-                                                                          methyl  "                                                             pentyl-1                                                             82  H     cyclohexyl                                                                              methyl  "    90-92                                          83  H     2-methylcyclo-                                                                          methyl  "                                                             hexyl                                                                84  H     3-methylcyclo-                                                                          methyl  "                                                             hexyl                                                                85  H     3-trifluoro-                                                                            methyl  "                                                             methylcyclohexyl                                                     86  H     cyclohexylmethyl                                                                        methyl  "    138-140                                        87  H     benzyl   methyl  "    160-161                                        88  H     2-phenylethyl                                                                           methyl  "    181-182                                        89  H     bicyclo 2.2.1!-                                                                         methyl  "    127-130                                                  heptyl-2                                                                       (= norbonyl)                                                         90  H     adamantyl                                                                               methyl  "    202-203                                        91  H     cycloheptyl                                                                             methyl  "                                                   92  H     cyclooctyl                                                                              methyl  "    145-147                                        93  H     phenyl   ethyl   "                                                   94  H     phenyl   isopropyl                                                                              "    103-104                                        95  H     phenyl   tert-butyl                                                                             "                                                   96  H     methyl   tert-butyl                                                                             "                                                   97  H     methyl   phenyl  "    168-169                                        98  methyl                                                                               methyl   methyl  "    118-119                                        99  methyl                                                                               ethyl    methyl  "    oil                                            100 methyl                                                                               isopropyl                                                                               methyl  "    96-98                                          101 methyl                                                                               sec-butyl                                                                               methyl  "    oil                                            102 methyl                                                                               1-methoxy-                                                                              methyl  "                                                             2-propyl                                                             103 methyl                                                                               1-methoxy-2-                                                                            methyl  "                                                             butyl                                                                104 methyl                                                                               tert-butyl                                                                              methyl  "                                                   105 methyl                                                                               cyclohexyl                                                                              methyl  "    118-119                                        106 methyl                                                                               phenyl   methyl  "    oil                                            107 ethyl ethyl    methyl  "    90-92                                          108 ethyl cyclohexyl                                                                              methyl  "    109-110                                        109 ethyl phenyl   methyl  "    oil                                            110 1-methoxy-                                                                           phenyl   methyl  "                                                       2-propyl                                                                   111 isopropyl                                                                            phenyl   methyl  "    91-92                                          __________________________________________________________________________     No. R.sup.2 +  R.sup.3                                                                            R.sup.5 R.sup.6                                                                             m.p. (°C.)                              __________________________________________________________________________     112 tetramethylene methyl  OCH.sub.3                                                                           133-134                                        113 pentamethylene methyl  "    101-102                                        114 hexamethylene  methyl  "    oil                                            115 3-oxapentamethylene                                                                           methyl  "    89-90                                          116 3-iminopentamethylene                                                                         methyl  "                                                   __________________________________________________________________________     No. R.sup.2                                                                              R.sup.3  R.sup.5 R.sup.6                                                                             m.p. (°C.)                              __________________________________________________________________________     117 methyl                                                                               n-butyl  methyl  OCH.sub.3                                                                           oil                                            118 methyl                                                                               isobutyl methyl  "    oil                                            119 H     2-methoxy-5-                                                                            methyl  "                                                             nitrophenyl                                                          120 1-methoxy-                                                                           2-methyl-                                                                               methyl  "                                                       2-propyl                                                                             phenyl                                                               121 1-methoxy-                                                                           4-methyl-                                                                               methyl  "                                                       2-propyl                                                                             phenyl                                                               122 methyl                                                                               3-methoxy-                                                                              methyl  "    oil                                                      phenyl                                                               123 H     phenyl   methyl  methyl                                                                              247                                            124 H     phenyl   hydrogen                                                                               methyl                                              125 H     phenyl   trifluoromethyl                                                                        methyl                                              126 H     2-methoxy-5-                                                                            methyl  OCH.sub.3                                                                           253-254                                                  chlorophenyl                                                         127 H     sec-butyl                                                                               methyl  methyl                                              128 H     tert-butyl                                                                              methyl  methyl                                              129 H     tert-butyl                                                                              methyl  trifluoro-                                                                     methyl                                              130 H     tert-butyl                                                                              trifluoro-                                                                             methyl                                                                 methyl                                                      131 H     cyclohexyl                                                                              methyl  methyl                                                                              more than                                                                      250                                            132 H     2-fluoro-                                                                               methyl  methyl                                                                              250-252                                                  phenyl                                                               133 H     2-fluoro-                                                                               methyl  methyl                                                        phenyl                                                               134 H     2-azaphenyl                                                                             methyl  methyl                                              135 H     3-azaphenyl                                                                             methyl  methyl                                              136 H     phenyl   methyl  amino                                                                               more than                                                                      250                                            137 H     phenyl   methyl  methyl-                                                                        amino                                               138 H     phenyl   methyl  dimethyl-                                                                      amino                                               139 H     tert-butyl                                                                              methyl  amino                                               140 H     sec-butyl                                                                               methyl  methyl-                                                                        amino                                               __________________________________________________________________________

EXAMPLE 8 1-acetyl-3-anilino-4-methoxycarbonyl-5-methylpyrazole

23 g of 3-anilino-4-methoxycarbonyl-5-methylpyrazole is dissolved in 51 g of acetic anhydride and brought to the boil. After 15 minutes' boiling the mixture is allowed to cool, poured into ice water and stirred for 30 minutes. The solid which separates is isolated and recrystallized from methanol; m.p. 115°-116° C.

The position of the acetyl group was determined by means of the IR spectrum (CO band at 1720 cm⁻¹).

This result merely rules cut that the anilino radical was acetylated. X-ray structural analysis has shown that the acetyl radical is in 1-position of the pyrazole ring.

EXAMPLE 9 1-acetyl-3-cyclohexylamino-4-methoxycarbonyl-5-methylpyrazole

This compound is prepared in a manner analogous to that described in Example 6, except that the starting materials are reacted at room temperature with cooling. The reaction lasts 1 hour; m.p. 140°-142° C.

Further derivatives of pyrazoles which have been obtained by one of the methods of the Examples or other prior art methods are listed in the following Table.

    __________________________________________________________________________      ##STR6##                                                                      No.                                                                               R.sup.1       R.sup.2                                                                              R.sup.3           R.sup.4                                                                               R.sup.5  m.p.                  __________________________________________________________________________                                                              (°C.)          141                                                                               formyl        hydrogen                                                                             phenyl            CO.sub.2 CH.sub.3                                                                     methyl                         142                                                                               formyl        "     sec-butyl         "      "                              143                                                                               formyl        "     tert-butyl        "      "                              144                                                                               acetyl        "     phenyl            "      "        116                   145                                                                               chloro-       "     phenyl            "      "        145-147                  acetyl                                                                      146                                                                               methyl-       "     "                 "      "        201-203                  sulfonyl                                                                    147                                                                               methyl-       "     "                 "      "        127                      amino-                                                                         carbonyl                                                                    148                                                                               tri-          "     "                 "      "                                 fluoro-                                                                        acetyl                                                                      149                                                                               propionyl     "     "                 "      "        120-122               150                                                                               benzyol       "     "                 "      "        155-156               151                                                                               methoxy-      "     "                 "      "        142                      carbonyl                                                                    152                                                                               ethoxycar-    "     "                 "      "        130-132                  bonyl                                                                       153                                                                               acetyl        "     2-methyl-         "      "        145-147                                      phenyl                                                  154                                                                               acetyl        "     3-methyl-         "      "        86-89                                        phenyl                                                  155                                                                               acetyl        "     2-fluoro-         "      "        144-146                                      phenyl                                                  156                                                                               acetyl        "     3-fluoro-         "      "        135-136                                      phenyl                                                  157                                                                               acetyl        "     4-fluoro-         "      "        132-134                                      phenyl                                                  158                                                                               acetyl        "     sec-butyl         "      "        76-77                 159                                                                               acetyl        "     tert-butyl        "      "        120                   160                                                                               acetyl        "     cyclopentyl       "      "        96-98                 161                                                                               acetyl        "     cyclohexyl        "      "        140-142               162                                                                               acetyl        "     norbonyl          "      "        139-142               163                                                                               acetyl        acetyl                                                                               cyclohexyl        "      "        110-112               164                                                                               acetyl        methyl                                                                               cyclohexyl        "      "        80-82                 165                                                                               acetyl        "     phenyl            "      "        88-90                 166                                                                               "             hydrogen                                                                             tert-butyl        acetyl "        146                   167                                                                               "             methyl                                                                               "                 "      "                              168                                                                               "             hydrogen                                                                             phenyl            "      "        140-142               169                                                                               "             methyl                                                                               "                 "      "                              170                                                                               "             hydrogen                                                                             2-fluoro-         "      "                                                     phenyl                                                  171                                                                               "             "     cyclohexyl        "      "                              172                                                                               "             "     tert-butyl        tri-   "                                                                       fluoro-                                                                        acetyl                                173                                                                               trifluoro-    "     "                 tri-   "                                 acetyl                                fluoro-                                                                        acetyl                                174                                                                               methoxy-      "     phenyl            acetyl "                                 carbonyl                                                                    175                                                                               methoxy-      "     tert-butyl        methoxy-                                                                              "                                 carbonyl                              carbonyl                              176                                                                               ethoxy-       "     "                 methoxy-                                                                              "                                 carbonyl                              carbonyl                              177                                                                               methoxy-      "     "                 acetyl "                                 carbonyl                                                                    178                                                                               cyano         "     phenyl            "      "                              179                                                                               "             "     "                 methoxy-                                                                              "                                                                       carbonyl                              180                                                                               acetyl        "     "                 cyano  "                              181                                                                               "             methyl                                                                               ethyl             methoxy-                                                                              "        41-41                                                          carbonyl                              182                                                                               "             "     isopropyl         methoxy-                                                                              "        75-76                                                          carbonyl                              183                                                                               "             "     n-butyl           methoxy-                                                                              "                                                                       carbonyl                              184                                                                               "             "     iso-butyl         methoxy-                                                                              "                                                                       carbonyl                              185                                                                               "             "     sec-butyl         methoxy-                                                                              "        51-53                                                          carbonyl                              186                                                                               "             "     tert-butyl        methoxy-                                                                              "                                                                       carbonyl                              187                                                                               "             ethyl phenyl            methoxy-                                                                              "        71-72                                                          carbonyl                              188                                                                               "             isopropyl                                                                            "                 methoxy-                                                                              "                                                                       carbonyl                              189                                                                               "             1-methoxy-                                                                           "                 methoxy-                                                                              "                                               2-propyl                carbonyl                              190                                                                               "             1-methoxy-                                                                           2-methyl-         methoxy-                                                                              "                                               2-propyl                                                                             phenyl            carbonyl                              191                                                                               "             1-methoxy-                                                                           4-methyl-         methoxy-                                                                              "                                               2-propyl                                                                             phenyl            carbonyl                              192                                                                               "             3-methoxy-                                                                           methyl            methoxy-                                                                              "                                               phenyl                  carbonyl                              193                                                                               "             4-methoxy-                                                                           H                 methoxy-                                                                              "        126-128                                phenyl                  carbonyl                              194                                                                                ##STR7##     H     C.sub.4 H.sub.9 sec                                                                              COOCH.sub.3                                                                           CH.sub.3 63                    195                                                                               H             H                                                                                     ##STR8##                                                                                         ##STR9##                                                                             CH.sub.3 196                   196                                                                               H             H                                                                                     ##STR10##                                                                                        ##STR11##                                                                            CH.sub.3 105-107               197                                                                               H             H                                                                                     ##STR12##        CCOC.sub.2 H.sub.5                                                                    H                              198                                                                               H             H                                                                                     ##STR13##        COOCH.sub.3                                                                           CH.sub.3 oil                   199                                                                               H             H     1-methoxy-        dimethyl-                                                                             methyl                                                propyl            carbamoyl                             200                                                                               H             H     3-hydroxy-        CO.sub.2 C.sub.2 H.sub.5                                                              "        215-217                                      phenyl                                                  201                                                                               H             H     phenyl            CO.sub.2 CH.sub.3                                                                     phenyl   139-140               202                                                                               phenoxy-      H     "                 "      methyl   136-138                  carbonyl                                                                    203                                                                               acetyl        CH.sub.3                                                                             1-methoxy-        "      "        52-53                                        2-propyl                                                204                                                                               H             H     3-fluoro-         "      H        160                                          phenyl                                                  205                                                                               H             H     2-fluoro-         "      "                                                     phenyl                                                  206                                                                               H             H     3-methoxy-        "      "                                                     phenyl                                                  207                                                                               H             H     phenyl            "      methoxy- 125-126                                                               methyl                         208                                                                               H             H     phenyl            "      chloro-  156-157                                                               methyl                         209                                                                               H             H     phenyl            "      CH.sub.2CO.sub.2 CH.sub.3                                                               156- 157              210                                                                               H             H     "                 "      CO.sub.2 CH.sub.3              211                                                                               H             H     tert-butyl        "      Br                             212                                                                               H             H     2,3-dichloro-     "      CH.sub.3 253-255                                      phenyl                                                  213                                                                               H             H     2,3-dimethyl-     "      "        216-218                                      phenyl                                                  214                                                                               H             H     2-cyanophenyl     "      "                              215                                                                               H             H     3-nitrophenyl     "      "                              216                                                                               H             H     3-methoxy-        "      "                                                     carbonylphenyl                                          217                                                                               H             H     2-chloro-5-       "      "        more than                                    trifluoromethyl-         240                                                   phenyl                                                  218                                                                               H             H     2,5-dimethoxy-    "      "        180-181                                      phenyl                                                  219                                                                               H             H     2-methoxy-5-      "      "        192                                          methylphenyl                                            220                                                                               acetyl        H     sec-butyl         COOCH.sub.3                                                                           H        76-77                 223                                                                               "             H     phenyl            CO.sub.2 C.sub.3 H.sub.7                                                              CH.sub.3 121                   224                                                                               "             H     "                 CO.sub.2 CH.sub.3                                                                     CH.sub.2CO.sub.2 CH.sub.3                                                               142-143               225                                                                                ##STR14##    H     phenyl            "      CH.sub.3 165-166               226                                                                               H             H     phenyl            CN     CH.sub.3 221-222               227                                                                               H             H     3-methyl-4-       CO.sub.2 CH.sub.3                                                                     CH.sub.3 192-194                                      fluorophenyl                                            228                                                                               acetyl        H     3-methyl-4-       "      "        115                                          fluorophenyl                                            229                                                                               acetyl        H     2-methyl-4-       "      "        163-164                                      fluorophenyl                                            230                                                                               H             H     2-methyl-5-       "      "        230-232                                      fluorophenyl                                            231                                                                               acetyl        H     2-methyl-5-       "      "        191-192                                      chlorophenyl                                            232                                                                               acetyl        H     3,4-dichloro-     "      "        142-143                                      phenyl                                                  233                                                                               acetyl        H     4-methyl-         "      "        130-132                                      phenyl                                                  234                                                                               "             H     4-chloro-         "      "        150-153                                      phenyl                                                  235                                                                               "             H     α-phenyl-   "      "        92-93                                        ethyl                                                   236                                                                               "             H                                                                                     ##STR15##        "      "        135-136               237                                                                               "             H     2,5-dimethoxy-    "      "        177-178                                      phenyl                                                  238                                                                               "             H     2-methoxy-5-      "      "        221-223                                      chlorophenyl                                            239                                                                               "             H     2,3-dichloro-     "      "        124-125                                      phenyl                                                  240                                                                               "             H     2,5-dichloro-     "      "        180-182                                      phenyl                                                  241                                                                               "             H     2-trifluoro-      "      "        147-148                                      methylphenyl                                            242                                                                               H             H                                                                                     ##STR16##        "      "        153                   243                                                                               H             n-C.sub.3 H.sub.7                                                                    n-C.sub.3 H.sub.7 "      "        56-58                 244                                                                               H             H                                                                                     ##STR17##        "      "        oil                   245                                                                               H             H                                                                                     ##STR18##        "      "        amorphous glass       246                                                                               H             H     2,4-difluoro-     "      "        184-185                                      phenyl                                                  247                                                                               H             H     2,5-difluoro-     "      "        222                                          phenyl                                                  248                                                                               2,4-dichloro- H     phenyl            "      "        197-198                  phenoxyacetyl                                                               249                                                                               α-(2,4-dichloro-                                                                       H     phenyl            "      "        152-154                  phenoxy)                                                                       propionyl                                                                   250                                                                               H             CH.sub.3                                                                             3-methoxyphenyl   "      "        oil                   251                                                                               phenoxy-      H     pentyl-3-         "      "        94-96                    carbonyl                                                                    252                                                                               dimethylcarbonyl                                                                             H     phenyl            "      "        136                   253                                                                                ##STR19##    H     "                 "      "        165-167               254                                                                                ##STR20##    H     phenyl            "      "        102                   255                                                                               phenoxy-      H     3-methoxyphenyl   "      "        165-166                  carbonyl                                                                    256                                                                               p-toluyl-     H     phenyl            "      "                                 sulfonyl                                                                    __________________________________________________________________________

EXAMPLE 10

The sulfur-containing hydrochloride obtained from 14.7 g of 4-tert-butylthiosemicarbazide and 15.1 g of methyl 2-chloroacetate in 200 ml of tetrahydrofuran is suspended in 100 ml of methanol and boiled. On cooling, the solution filtered hot separates the hydrochloride from 3-tert-butylamino-4-methoxycarbonyl-5-methylpyrazole. Colorless crystals, m.p. 178° C.

The following compounds were prepared analogously.

    ______________________________________                                         No.  R.sup.1                                                                              R.sup.2                                                                               R.sub.3                                                                             R.sup.4 R.sup.5                                                                             salt   m.p. (°C.)                   ______________________________________                                         221  H     CH.sub.3                                                                              C.sub.2 H.sub.5                                                                     COOCH.sub.3                                                                            CH.sub.3                                                                            hydro- 147-149                                                                 chloride                                   222  H     CH.sub.3                                                                              2-n- COOCH.sub.3                                                                            CH.sub.3                                                                            hydro- 173-175                                               butyl             chloride                                   ______________________________________                                    

Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure a fine distribution of the active ingredient.

For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenol polyglycol ethers, alkylaryl polyester alcohols, isotridecyl alcohols, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient.

The new compounds exhibit herbicidal action and are suitable for removing or suppressing unwanted plant growth in crops or on non-crop land. It is natural that individual active ingredients have varying intensities or differ in their effect on unwanted plants or crop plants. Their influence on unwanted plants is illustrated in the Tables below. The series of experiments were carried out in the greenhouse and in the open.

I. Greenhouse experiments

Plastic flowerpots having a volume of 300 cm³ were filled with a loamy sand containing about 1.5% of humus. The seeds of the test plants according to Table 1, split up into species, were sown shallowly therein. Immediately afterwards, in the case of preemergence treatment, the active ingredients were applied to the surface of the soil. They were suspended or emulsified in water as distributing agent and sprayed onto the soil by means of atomizing nozzles. After the agents had been applied, the pots were lightly sprinkler-irrigated in order to stimulate germination and growth of the plants and at the same time activate the chemical agents. The pots were then covered with transparent plastic hoods until the plants had emerged. The covering effected uniform germination of the test plants, where this was not impaired by the chemicals, and prevented readily volatile active ingredients from evaporating.

For the purpose of the postemergence treatment, the plants were first grown to a height of 3 to 10 cm, depending on their habit, in the pots and then treated. They were not covered. The tests were carried out in a greenhouse, the warmer sections of the greenhouse (25° to 40° C.) being preferred for the warmth-loving species and 15° to 30° C. for those of temperature climates. The experimental period was from 4 to 6 weeks. During this period the plants were tended and their reactions to the various treatments were evaluated. The following tables contain the test substances, the various rates of application in kg/ha of active substance and the species of test plants. Assessment is on a scale of 0 to 100, 0 denoting no damage or normal emergence and 100 denoting no emergence of the plants or complete destruction at least of the parts of the shoots above the ground.

II. Experiments in the open

These were experiments on small plots at locations with loamy sand of pH 5-6 and a humus content of 1 to 1.5%. Postemergence treatments are described which have been carried out on young test plants in the early growth stages up to a height of 5 cm. The weed flora of the most varied species was governed by the time of year (e.g. spring-germinating species and summer-germinating species). The compounds were emulsified or suspended in water as carrier and distribution medium and applied with the aid of a motor-driven plot spray mounted on a hitch. When there was no natural precipitation, the plots were sprinkler-irrigated in order to ensure the germination and growth of the plants. All the experiments lasted several weeks. Then the evaluation was carried out using the scale 0 to 100.

Results

Tables 2 to 13 contain the results of the experiments.

It has become evident that the new 3-aminopyrazole derivatives have interesting herbicidal properties in pre- and postemergence application and differ from the comparative agents.

What is particularly striking is the broad spectrum of action, numerous unwanted broadleaved and grass plants being controlled. In this aspect, in particular, the new compounds offer substantial advantages over the prior art comparative active ingredients.

There are various ways of applying the compounds of the invention.

1. The agents may be used for the selective control of unwanted plants in various crops, including ornamental lawns, e.g. Bermudagrass (Table 6). The latter may be monocotyledonous or dicotyledonous herbaceous crop plants, the agents also coming into direct contact with the leaves or the leaves of the crop plants. However, application techniques may also be used in which spraying equipment is used that enables the agents to be sprayed in such a way that the leaves of sensitive crop plants are not touched if possible and the agents come into contact only with the soil beneath or the unwanted plants growing in it (post-directed or lay-by).

2. The broad spectrum of species from the most varied families that can be controlled also means that the agents are suitable for destroying unwanted broadleaves and grass weeds in woody trees and bushes as well as sugar cane.

3. Furthermore the agents can be used on non-crop areas such as industrial and railroad areas, parking and storage areas, paths, edges of ditches, and forest cutover land. Here it is more a question of the application rate whether the plants are completely eliminated or merely have their growth suppressed and retarded without the plants dying.

4. The compounds tested include those that are suitable for drying green leaves and stems (desiccants). Such agents are used for example for killing potato tops before the mechanical potato harvest, for controlling weeds that break through in ripe cereal fields before the harvest, for accelerating the drying of soya beans before combine harvesting, and for removing green vegetation in cotton which is ready for picking before the harvest.

In view of the variety of application methods the agents of the invention or compositions containing same may be used for removing unwanted plant growth in a large number of crop in addition to those listed in the Tables. The rates of application may vary from 0.1 to 15 kg/ha or more depending on the object to be controlled.

The following are examples of crop plants.

    ______________________________________                                         Botanical name      English term                                               ______________________________________                                         Allium cepa         onions                                                     Ananas comosus      pineapple                                                  Arachis hypogaea    peanuts (groundnuts)                                       Asparagus officinalis                                                                              asparagus                                                  Avena sativa        oats                                                       Beta vulgaris spp. altissima                                                                       sugarbeets                                                 Beta vulgaris spp. rapa                                                                            fodder beets                                               Beta vulgaris spp. esculenta                                                                       table beets, red beets                                     Brassica napus var. napus                                                                          rape                                                       Brassica napus var. napobrassica                                               Brassica napus var. rapa                                                                           turnips                                                    Brassica rapa var. silvestris                                                  Carmellia sinensis  tea plants                                                 Carthamus tinctorius                                                                               safflower                                                  Citrus limon        lemon                                                      Citrus maxima       grapefruits                                                Citrus reticulata                                                              Citrus sinensis     orange trees                                               Coffea arabica (Coffea canephora,                                                                  coffee plants                                              Coffea liberica)                                                               Cucumis melo        melons                                                     Cucumis sativus     cucumber                                                   Cynodon dactylon    Bermudagrass in turfs                                                          and lawns                                                  Daucus carota       carrots                                                    Elaeis guineensis   oil palms                                                  Fragaria vesca      strawberries                                               Glycine max         soybeans                                                   Gossypium hirsutum  cotton                                                     (Gossypium arboreum                                                            Gossypium herbaceum                                                            Gossypium vitifolium)                                                          Helianthus annuus   sunflowers                                                 Helianthus tuberosus                                                           Hevea brasiliensis  rubber plants                                              Hordeum vulgare     barley                                                     Humulus lupulus     hop                                                        Ipomoea batatas     sweet potato                                               Lactuca sativa      lettuce                                                    Lens culinaris      lentils                                                    Linum usitatissimum flax                                                       Lycopersicon lycopersicum                                                                          tomato                                                     Malus spp.          apple trees                                                Manihot esculenta   cassava                                                    Medicago sativa     alfalfa (lucerne)                                          Mentha piperita     peppermint                                                 Musa spp.           banana plants                                              Nicotiana tabacum   tobacco                                                    (N. rustica)                                                                   Olea europaea       olive trees                                                Oryza sativa        rice                                                       Panicum miliaceum                                                              Phaseolus lunatus   limabeans                                                  Phaseolus mungo     mungbeans                                                  Phaseolus vulgaris  snapbeans, green beans,                                                        dry beans                                                  Pennisetum glaucum                                                             Petroselinum crispum                                                                               parsley                                                    spp. tuberosum                                                                 Picea abies         Norway spruce                                              Abies alba          fire                                                       Pinus spp.          pine trees                                                 Pisum sativum       English peas                                               Prunnus avium       cherry trees                                               Prunus domestica    plum trees                                                 Prunus persica      peach trees                                                Pyrus communis      pear trees                                                 Ribes sylvestre     red currants                                               Ribes uva-crispa                                                               Ricinus communis                                                               Saccharum officinarum                                                                              sugar cane                                                 Secale cereale      rye                                                        Sesamum indicum     Sesame                                                     Solanum tuberosum   Irish potatoes                                             Sorghum bicolor (s. vulare)                                                                        grain sorghum                                              Sorghum dochna                                                                 Spinacia oleracea   spinach                                                    Theobroma cacao     cacao plants                                               Trifolium pratense  red clover                                                 Tritioum aestivum   wheat                                                      Vaceinium corymbosum                                                                               blueberry                                                  Vaccinium vitis-idaea                                                                              cranberry                                                  Vicia faba          tick beans                                                 Vigna sinensis (V. unguiculata)                                                                    cow peas                                                   Vitis vinifera      grapes                                                     Zea mays            Indian corn, sweet corn,                                                       maize                                                      ______________________________________                                    

To further increase the spectrum of action of the new individual active ingredients, to achieve synergistic effects or to improve persistence in the soil, numerous other herbicidal compounds and growth regulators may be used as components for mixtures and combination. Depending on the area of use and the unwanted plants to be controlled, the following substances or similar derivatives are suitable as components:

    ______________________________________                                          ##STR21##                                                                     R              R.sup.1      R.sup.2                                            ______________________________________                                          ##STR22##     NH.sub.2     Cl                                                  ##STR23##     NH.sub.2     Br                                                  ##STR24##     OCH.sub.3    OCH.sub.3                                           ##STR25##     OCH.sub.3    OCH.sub.3                                           ##STR26##     NH.sub.2     Cl                                                  ##STR27##     NHCH.sub.3   Cl                                                  ##STR28##     NH.sub.2     Br                                                  ##STR29##     NH.CH.sub.3  Cl                                                 ______________________________________                                          ##STR30##                                                                     R             R.sup.1     R.sup.2                                              ______________________________________                                                        ##STR31##  H salts                                              H                                                                                             ##STR32##  CH.sub.3 salts                                       H                                                                                             ##STR33##  Cl salts                                             H                                                                                             ##STR34##  F salts                                              CH.sub.2 OCH.sub.3                                                                            ##STR35##  F                                                     ##STR36##              salts                                                                                    ##STR37##                                    ______________________________________                                          ##STR38##                                                                     R     R.sup.1   R.sup.2                                                                               R.sup.3     R.sup.4                                     ______________________________________                                         H     F.sub.3 C H      C.sub.2 H.sub.5                                                                            C.sub.4 H.sub.9                             H     F.sub.3 C H      n.C.sub.3 H.sub.7                                                                          n.C.sub.3 H.sub.7                           H     F.sub.3 C H      CH.sub.2CH.sub.2 Cl                                                                        n.C.sub.3 H.sub.7                           H     SO.sub.2 NH.sub.2                                                                        H      n.C.sub.3 H.sub.7                                                                          n.C.sub.3 H.sub.7                           H     F.sub.3 C H      nC.sub.3 H.sub.7                                                                            ##STR39##                                  H.sub.3 C                                                                            H.sub.3 C H      H                                                                                           ##STR40##                                  ______________________________________                                          ##STR41##                                                                     R               R.sup.1                                                                               R.sup.2                                                 ______________________________________                                          ##STR42##      H      iC.sub.3 H.sub.7                                        CH.sub.3        H                                                                                      ##STR43##                                               ##STR44##      H                                                                                      ##STR45##                                               ##STR46##      H      iC.sub.3 H.sub.7                                         ##STR47##      H                                                                                      ##STR48##                                               ##STR49##      H      CH.sub.3                                                ______________________________________                                          ##STR50##                                                                     R                R.sup.1     R.sup.2                                           ______________________________________                                          ##STR51##       H           CH.sub.3                                           ##STR52##       H           C.sub.2 H.sub.5                                    ##STR53##       CH.sub.3    CH.sub.3                                           ##STR54##       H           CH.sub.3                                          ______________________________________                                          ##STR55##                                                                     R           R.sup.1    R.sup.2                                                 ______________________________________                                         iC.sub.3 H.sub.7                                                                           iC.sub.3 H.sub.7                                                                          CH.sub.2CClCCl.sub.2                                    iC.sub.3 H.sub.7                                                                           iC.sub.3 H.sub.7                                                                          CH.sub.2CClCHCl                                         n.C.sub.3 H.sub.7                                                                          n.C.sub.3 H.sub.7                                                                         C.sub.2 H.sub.5                                         ______________________________________                                          ##STR56##                                                                     R                  X     Y      R.sup.1                                        ______________________________________                                         CH.sub.3           Cl    Cl     Na                                              ##STR57##         Cl  H Cl CH.sub.3                                                                           Na CH.sub.3                                     ##STR58##         H     CH.sub.3                                                                               ##STR59##                                      ##STR60##         H     CH.sub.3                                                                              Na                                              ##STR61##         H     CH.sub.3                                                                              Na                                             ______________________________________                                          ##STR62##                                                                     R            R.sup.1        R.sup.2                                            ______________________________________                                          ##STR63##   H                                                                                              ##STR64##                                          ##STR65##   H              C.sub.2 H.sub.5                                     ##STR66##                                                                                   ##STR67##     CH.sub.2 Cl                                         ##STR68##                                                                                   ##STR69##     CH.sub.2 Cl                                         ##STR70##   CH.sub.2OCH.sub.3                                                                             CH.sub.2 Cl                                         ##STR71##                                                                                   ##STR72##     CH.sub.2 Cl                                         ##STR73##   iC.sub.3 H.sub.7                                                                              CH.sub.2 Cl                                         ##STR74##   CH.sub.2CH.sub.2OCH.sub.3                                                                     Cl.sub.2 Cl                                        C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                                ##STR75##                                          ##STR76##   H                                                                                              ##STR77##                                          ##STR78##   H              CH.sub.3                                            ##STR79##   H              CH.sub.3                                           ______________________________________                                          ##STR80##                                                                     R       R.sup.1   X         R.sup.2                                                                              R.sup.3                                      ______________________________________                                         H       C.sub.2 H.sub.5                                                                          SCH.sub.3 H     C.sub.2 H.sub.5                              H       iC.sub.3 H.sub.7                                                                         SCH.sub.3 H     C.sub.2 H.sub.5                              H       iC.sub.3 H.sub.7                                                                         Cl        H     C.sub.2 H.sub.5                              H       iC.sub.3 H.sub.7                                                                         Cl        H                                                                                     ##STR81##                                   H       C.sub.2 H.sub.5                                                                          Cl        H     C.sub.2 H.sub.5                              H       C.sub.2 H.sub.5                                                                          Cl        H                                                                                     ##STR82##                                   H       iC.sub.3 H.sub.7                                                                         OCH.sub.3 H     iC.sub.3 H.sub.7                             ______________________________________                                          ##STR83##                                                                     X           Y         R                                                        ______________________________________                                         Br          Br        H salts                                                  I           I         H salts                                                  Br          Br                                                                                        ##STR84##                                                ##STR85##                                                                      ##STR86##                                                                     ______________________________________                                          ##STR87##                                                                     R               R.sup.1                                                                               R.sup.2 R.sup.3                                         ______________________________________                                          ##STR88##      H      CH.sub.3                                                                               CH.sub.3                                         ##STR89##      H      CH.sub.3                                                                               CH.sub.3                                         ##STR90##      H      CH.sub.3                                                                               CH.sub.3                                         ##STR91##      CH.sub.3                                                                              CH.sub.3                                                                               H                                                ##STR92##      H      CH.sub.3                                                                               CH.sub.3                                         ##STR93##      H      CH.sub.3                                                                               CH.sub.3                                         ##STR94##      H      CH.sub.3                                                                                ##STR95##                                       ##STR96##      H      CH.sub.3                                                                               OCH.sub.3                                        ##STR97##      H      CH.sub.3                                                                               CH.sub.3                                         ##STR98##      H      CH.sub.3                                                                               CH.sub.3                                         ##STR99##      H      CH.sub.3                                                                               OCH.sub.3                                        ##STR100##     H      CH.sub.3                                                                               CH.sub.3                                         ##STR101##     H      CH.sub.3                                                                               CH.sub.3                                         ##STR102##     H      CH.sub.3                                                                               OCH.sub.3                                        ##STR103##     H      CH.sub.3                                                                               H                                                ##STR104##     CH.sub.3                                                                              CH.sub.3                                                                               H                                                ##STR105##     CH.sub.3                                                                              CH.sub.3                                                                               H                                                ##STR106##     H      C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                  ##STR107##     H      CH.sub.3                                                                               CH.sub.3                                         ##STR108##                                                                    ______________________________________                                          ##STR109##                                                                    R          R.sup.1   R.sup.2  R.sup.3                                          ______________________________________                                         Cl         CF.sub.3  H        COOH salts                                       Cl         Cl        H        H                                                Cl         Cl        H                                                                                        ##STR110##                                      H          CF.sub.3  Cl       OC.sub.2 H.sub.5                                  ##STR111##                                                                    ______________________________________                                          ##STR112##                                                                    R                R.sup.1     R.sup.2                                           ______________________________________                                         tert.-C.sub.4 H.sub.9                                                                           NH.sub.2    SCH.sub.3                                          ##STR113##      NH.sub.2    CH.sub.3                                           ##STR114##      NH.sub.2    SCH.sub.3                                          ##STR115##                                                                    ______________________________________                                          ##STR116##                                                                    R          R.sup.1   R.sup.2  R.sup.3                                          ______________________________________                                         H          CH.sub.3  Br                                                                                       ##STR117##                                      H          CH.sub.3  Br       iC.sub.3 H.sub.7                                 H          CH.sub.3  Cl       tert.-C.sub.4 H.sub.9                            H          CH.sub.3  Cl                                                                                       ##STR118##                                       ##STR119##                                                                    ______________________________________                                          ##STR120##                                                                    X                Y           R                                                 ______________________________________                                         CF.sub.3         H           CH.sub.3                                          H                F           CH.sub.3                                           ##STR121##                                                                     ##STR122##                                                                     ##STR123##                                                                    ______________________________________                                          ##STR124##                                                                    R      R.sup.1                                                                               R.sup.2  R.sup.3                                                                               R.sup.4                                          ______________________________________                                         H      Cl     NH.sub.2 Cl     H salts, esters, amides                          Cl     Cl     H        Cl     Na                                               Cl     H      Cl       OCH.sub.3                                                                             H salts, esters, amides                          Cl     Cl     H        Cl     H.(CH.sub.3).sub.2 NH                            ______________________________________                                          ##STR125##                                                                    R             R.sup.1   R.sup.2                                                ______________________________________                                          ##STR126##   CH.sub.3 H salts, esters, amides                                  ##STR127##   H        H salts, esters, amides                                  ##STR128##   H        H salts, esters, amides                                  ##STR129##   H        H salts, esters, amides                                  ##STR130##   CH.sub.3 H salts, esters, amides                                  ##STR131##   CH.sub.3 H salts, esters, amides                                  ##STR132##   H        H salts, esters, amides                                 ______________________________________                                          ##STR133##                                                                    R                 R.sup.1                                                      ______________________________________                                          ##STR134##       H salts, esters, amides                                       ##STR135##       H salts, esters, amides                                       ##STR136##                                                                     ##STR137##                                                                     ##STR138##                                                                     ##STR139##                                                                     ##STR140##                                                                     ##STR141##                                                                     ##STR142##                                                                    ______________________________________                                          ##STR143##                                                                    R               R.sup.1        R.sup.2                                         ______________________________________                                         COOCH.sub.3     COOCH.sub.3    Cl                                               ##STR144##     R = CN R = CSNH.sub.2                                           ##STR145##                                                                    ______________________________________                                          ##STR146##                                                                    R               R.sup.1     R.sup.2                                            ______________________________________                                         OH              CH.sub.3    Na                                                 CH.sub.3        CH.sub.3    Na                                                 CH.sub.3        CH.sub.3    OH                                                 ONa             CH.sub.3    Na                                                  ##STR147##                                                                     ##STR148##                                                                     ##STR149##                                                                     ##STR150##                                                                     ##STR151##                                                                     ##STR152##                                                                     ##STR153##                                                                     ##STR154##                                                                     ##STR155##                                                                    NH.sub.4 SCN                                                                    ##STR156##                                                                     ##STR157##                                                                     ##STR158##                                                                     ##STR159##                                                                     ##STR160##                                                                    ______________________________________                                    

It is also advantageous to apply the compounds of the invention either alone or in combination with other herbicides, in admixture with other crop protection agents, for example agents for combatting pest or phytopathogenic fungi or bacteria. Of further interest is the fact that the compounds of the invention may be mixed with solutions of mineral fertilizers used to eliminate trace element or nutritional deficiencies.

Spreader-stickers and non-phytothoxic oils may be added to the compounds of the invention to ensure that they take effect. ##STR161##

                  TABLE 1                                                          ______________________________________                                         List of test plants                                                            Botanical name   English term                                                  ______________________________________                                         Abutilon theoprasti                                                                             velvet leaf                                                   Amaranthus retroflexus                                                                          redroot pigweed                                               Carthamus tinctorius                                                                            safflower                                                     Chenopodium album                                                                               lambsquarters (goosefoot)                                     Centaurea cyanus cornflower                                                    Cynodon dactylon Bermudagrass                                                  Cyperus difformis                                                                               smallflower umbrellaplant                                     Datura atramonium                                                                               Jimsonweed                                                    Daucus carota    carrots                                                       Echinochloa crus galli                                                                          barnyardgrass                                                 Euphorbia geniculata                                                                            Southamerican member of the                                                    spurge family                                                 Galium aparine   catchweed bedstraw                                            Helianthus annuus                                                                               sunflower                                                     Ipomoea spp.     morningglory                                                  Lamium purpureum red deadnettle                                                Lolium multiflorum                                                                              annual raygrass                                               Matricaria spp.  chamomile                                                     Mercurialis annua                                                                               annual mercury                                                Pisum sativum    English peas                                                  Polygonum percicaria                                                                            ladystumb                                                     Polygonum aviculare                                                                             prostrate knotweed                                            Raphanus raphanistrum                                                                           wild radish                                                   Sesbania oxaltata                                                                               hemp sesbania                                                 Setaria spp.     foxtail spp.                                                  Sida spinosa     teaweed (prickly sida)                                        Sinapis alba     white mustard                                                 Sinapis arvensis yellow charlock                                               Solanum nigrum   black nightshade                                              Sorghum bicolor  Sorghum                                                       Sorghum halepense                                                                               Johnsongrass                                                  Stellaria media  chickweed                                                     Triticum aestivum                                                                               wheat                                                         Xanthium pensylvanicum                                                                          common cocklebur                                              Zea mays         Indian corn                                                   Alopecurus myosuroides                                                                          slender foxtail                                               Arachis hypogaea peanut (groundnuts)                                           Fragaria vesca   strawberries                                                  Gossypium hirsutum                                                                              cotton                                                        Lamium amplexicaule                                                                             henbit                                                        Portulaca oleracea                                                                              purslane                                                      ______________________________________                                    

                  TABLE 2                                                          ______________________________________                                         Herbicidal action of compounds on unwanted plants;                             preemergenece treatment in the greenhouse                                              Test plants and % damage                                                                       Euphor-                                                Com-                    bia  Ipo-                                              pound                   geni-                                                                               moea  Solanum                                                                               Sorghum                              no.   kg/ha             culata                                                                              spp.  nigrum halepense                            ______________________________________                                                       Echino-                                                                        chloa                                                                          crus                                                                           galli                                                            14    4.0     100      75     85   95     85                                   68    2.0      70     100     93   --     70                                   106   4.0     100     100    100   40     100                                  144   4.0     100     100    100   80     75                                   145   4.0     100     100     90   90     75                                   113   4.0      60     --      75   50     60                                                 Setaria                                                                        spp.                                                             29    4.0      40     --      95   90     20                                   59    4.0     100     --     100   95     90                                   80    4.0     100     --     100   95     100                                  89    4.0     100     --     100   95     70                                   69    4.0     100     --     100   75     95                                   ______________________________________                                          0 = no damage                                                                  100 = plants completely destroyed                                        

                                      TABLE 3                                      __________________________________________________________________________     Herbicidal action; postemergence treatment in the greenhouse                                                Test plants and % damage                          Compound                     Abutilon                                                                              Echinochloa                                                                          Datura  Setaria                                                                           Sida Solanum              no.                      kg/ha                                                                              theophrasti                                                                           crus galli                                                                           stramonium                                                                            spp.                                                                               spinosa                                                                             nigrum               __________________________________________________________________________     29                       1.0 100     0    100    100 100  100                                           2.0 100    30    100    100 100  100                  59                       1.0 100    40     40    --   50   40                                           2.0 100    65     60    --   70  100                  80                       1.0 100    --     40    100  20   50                                           2.0 100    75    100    100 100  100                  89                       1.0 100    75    100    100  80  100                                           2.0 100    75    100    100 100  100                  prior art  A                                                                          ##STR162##        1.0 2.0                                                                             15  18                                                                                0 0   32 48  0  20                                                                              7  25                                                                               65 70               prior art  B                                                                          ##STR163##        1.0 2.0                                                                            100 100                                                                                0 0  100 100                                                                                0  30                                                                             100 100                                                                             100 100              __________________________________________________________________________      0 = no damage                                                                  100 = plants completely destroyed                                        

                                      TABLE 4                                      __________________________________________________________________________     Herbicidal action; postemergence application in the greenhouse                           Test plants and % damage                                             Compound  Centaurea                                                                            Echinochloa                                                                          Galium                                                                             Ipomoea                                                                             Lolium                                                                               Polygonum                                 no.   kg/ha                                                                              cyanus                                                                               crus galli                                                                           aparine                                                                            spp. multiflorum                                                                          aviculare                                 __________________________________________________________________________     67    3.0 100   100   0   100  100   0                                         15    3.0 100   100   100 100  100   0                                         71    3.0 100   100   30  100  100   100                                       70    3.0 100   100   30  100  100   100                                       31    3.0 50    100   50  100  0     100                                       77    3.0 100   --    50  100  50    0                                         161   3.0 100   100   100 60   100   100                                       115   3.0 100   50    0   100  100   100                                       132   3.0 50    100   0   0    100   --                                        157   3.0 100   100   100 100  70    0                                         160   3.0 100   100   70  100  100   100                                       154   3.0 100   100   100 100  70    0                                         105   3.0 100   100   0   100  100   30                                        164   3.0 100   70    100 100  100   30                                        165   3.0 100   100   50  100  100   100                                       162   3.0 100   100   100 100  100   30                                        21    3.0 100   100   0   100  70    0                                         100   3.0 100   80    0   100  100   --                                        159   3.0 100   90    100 100  100   100                                       166   3.0 100   40    70  90   95    --                                        72    3.0 100   40    20  70   95    --                                        204   3.0 40    100   40  0    90    --                                        158   3.0 100   40    95  40   100   --                                        10    3.0 100   80    100 100  100   --                                        111   3.0 40    20    100 40   100   --                                        187   3.0 20    40    100 90   100   --                                        101   3.0 100   40    100 100  100   --                                        221   3.0 90    0     90  0    0     --                                        109   3.0 80    40    100 100  100   --                                        168   3.0 100   100   40  0    100   0                                         222   3.0 100   60    100 95   --    --                                        185   3.0 100   35    95  95   --    --                                        __________________________________________________________________________      0 = no damage                                                                  100 = completely destroyed                                               

                                      TABLE 5                                      __________________________________________________________________________     Herbicidal action; postemergence treatment in the open                                                   Test plants and % damage                                                                                Raphanus                                                                       raphanistrum/               Compound                  Chenopodium                                                                           Matricaria                                                                           Polygonum                                                                            Polygonum                                                                            Sinapis                                                                               Stellaria            no.                   kg/ha                                                                              album  spp.  convolvulus                                                                          persicaria                                                                           arvensis                                                                              media                __________________________________________________________________________      14                   2.0  80     20    30   --     70     70                                        4.0  90     40    50   --     80     95                  194                   2.0  98    68     70    65    80     98                                        4.0 100     88    95    95    98    100                   68                   2.0 100     90   --     75    85    100                                        4.0 100     98   --     80    90    100                   82                   2.0  98     50    90    60    80     95                                        4.0 100     95   100   --    100    100                  106                   2.0 100     65    90   --     90      95                                       4.0 100     90   100   --    100     95                  144                   2.0 100     60    95   --     95    100                                        4.0 100     90   100   --    100    100                  149                   2.0 100     60   100   --    100    100                                        4.0 100     80   100   --    100    100                  123                   2.0 100     15   --     75   --      95                                        4.0 100     20   --     90   --                           30                   2.0 100     20   --     80   --     100                                        4.0 100     40   --    100   --     100                   B                    2.0 100    100    80    40   100    100                  prior art             4.0 100    100    90   100   100    100                  prior art  C.                                                                         ##STR164##     2.0 88                                                                              50 88  22 57                                                                                20 95                                                                                30 62                                                                               -- 100 -- 83                  A                   2.0  90     90    60   --     60     40                  prior art                                                                            4.0              95 100     90   --     80    60                         __________________________________________________________________________      0 = no damage                                                                  100 = plants completely destroyed                                        

                  TABLE 6                                                          ______________________________________                                         Herbicidal action in Bermuda grass;                                            postemergence application in the greenhouse                                             Test plants and % damage                                                                      Amaranthus Cy-   Mer-                                  Com-                    retraflexus                                                                               perus curi-                                 pound          Cynodon  from rhizomes                                                                             dif-  alis                                  no.    kg/ha   dactylon (Bermuda grass)                                                                           formis                                                                               annua                                 ______________________________________                                          14    1.0     10       100         93    98                                          2.0     --       100         98    98                                   145    1.0      0       --         100   100                                          2.0      0       --         --    100                                    82    1.0     10       25         100   100                                          2.0     20       40         --    100                                   B      1.0      0       70         100    36                                   prior art                                                                             2.0     --       100        100    56                                   ______________________________________                                          0 = no damage                                                                  100 = plants completely destroyed                                        

                  TABLE 7                                                          ______________________________________                                         Selective herbicidal action in peas;                                           postemergence treatment in the greenhouse                                                Test plants and % damage                                                             Pis-                                                           Com-            um     Ipo- Matri-      Sina-                                                                               Stel-                             pound           sati-  moea caria Setaria                                                                              pis  laria                             no.     kg/ha   vum    spp. spp.  spp.  alba media                             ______________________________________                                         113     1.0     0      40   100   30    --   --                                        2.0     10     75   100   100   --   --                                30      1.0     0      60   0     40    100  100                                       2.0     10     65   0     75    100  100                               68      1.0     2      95   100   98    100  100                                       2.0     4      99   100   98    100  100                               14      1.0     12     90   7     98     90   95                                       2.0     20     100  7     98     95   95                               69      1.0     0      100  100   100   100  100                                       2.0     0      100  100   100   100  100                               B       1.0     10     43   100   0      98   98                               prior art                                                                              2.0     --     55   100   30     98   98                               C       1.0     15     0    20    --     80   90                               prior art                                                                              2.0     28     --   20    --    100  100                               ______________________________________                                          0 = no damage                                                                  100 = plants completely destroyed                                        

                                      TABLE 8                                      __________________________________________________________________________     Selective herbicidal action in safflower;                                      postemergence application in the greenhouse                                    Com-    Test plants and % damage                                               pound   Carthamus                                                                            Amaranthus                                                                           Euphorbia                                                                            Mercurialis                                                                          Sesbania                                                                            Sida                                                                               Solanum                                                                             Xanthium                         no. kg/ha                                                                              tinctorius                                                                           retroflexus                                                                          geniculata                                                                           annua exaltata                                                                            spinosa                                                                            nigrum                                                                              pensylvani                       __________________________________________________________________________     144 1.0 0     100   100   100   100  100 100  100                                  2.0 0     100   100   100   100  100 100  100                              28  1.0 --    100   50    30    98   --  --   --                                   2.0 0     100   70    100   95   --  --   --                               17  1.0 --    0     60    100   90   --  --   100                                  2.0 0     0     70    100   100  --  --   100                              14  1.0 0     100   90    98    95   100  82   89                                  2.0 0     100   96    98    100  100 100   98                              30  1.0 0     88    85    100   95   --   20   30                                  2.0 0     90    85    100   95   --  100    30                             __________________________________________________________________________      0 = no damage                                                                  100 = plants completely destroyed                                        

                                      TABLE 9                                      __________________________________________________________________________     Selective herbicidal action; postemergence treatment in the greenhouse          ##STR165##                                                                    __________________________________________________________________________                                           Test plants and                                                                % damage                                 Compound                                                                             Substituents                    Daucus                                                                             Holianthus                           no.   R.sup.1                                                                           R.sup.2                                                                            R.sup. 3 R.sup.4     kg/ha                                                                               carota                                                                            annuus                               __________________________________________________________________________      30                               1.0  0   0                                                                     2.0  0  10                                    41                               1.0 --  --                                                                     2.0 --  --                                   144                               1.0 --  15                                                                     2.0 --  20                                   149                               1.0 --  10                                                                     2.0 --  30                                   prior art D                                                                          CH.sub.3                                                                          CH.sub.3                                                                            ##STR166##                                                                              ##STR167## 1.0 2.0                                                                            -- --                                                                              -- --                                prior art E                                                                          CH.sub.3                                                                          CH.sub.3                                                                            ##STR168##                                                                             OH          1.0 2.0                                                                            -- --                                                                              -- --                                A                                 1.0 --  --                                   prior art                         2.0 --  --                                   C                                 1.0 30  100                                  prior art                         2.0 35  100                                  __________________________________________________________________________     Test plants and % damage                                                       Compound                                                                              Sorghum                                                                             Triticum                                                                             Zea Echinochloa                                                                           Euphorbia                                                                              Ipomoea                                                                             Lamium                               no.   bicolor                                                                              aestivum                                                                             mays                                                                               crus galli                                                                            geniculata                                                                            spp.  purpureum                            __________________________________________________________________________      30   0     10    10  20      85    60    80                                         10    23    10  27      85    65    80                                    41   --    --    10  10      40    52    10                                         --    0     20  10     50     100   20                                   144   --    0      0  70     100    95    95                                         --    --     0  100    100    95    95                                   149   --    --     0  100    100    90    95                                         --    --     0  100    100    100   95                                   prior art                                                                            --    0     --  70     --     --    --                                   D     --    0     --  80     --     20    --                                   prior art                                                                            --    --    --  10     --      0     0                                   E     --    --    --  --     --      0     0                                   prior art                                                                            5     0     10   0     100    15     0                                   A     5     0     10   0     100    15     0                                   prior art                                                                            0     12    10   0     --      0    100                                  C     10    18    15   0     --     --    100                                  __________________________________________________________________________                       Test plants and % damage                                                 Compound                                                                             Mercurialis                                                                          Polygonum                                                                            Sesbania                                                                             Setaria                                                                           Sinapis                                                                            Stellaria                                       no.   annua persicaria                                                                           exaltata                                                                            spp.                                                                               alba                                                                               media                               __________________________________________________________________________                  30   100   100    95  40  100 100                                                   100   100    95  75  100 100                                              41   100    60    60  20  100 --                                                    100    90    60  40  100 --                                              144   100   --    100  100 100 --                                                    100   --    100  100 --  --                                              149   100   --    100  95  100 --                                                    100   --    100  95  100 --                                              prior art                                                                            --    --    --   --   0  --                                              D      30   --    --   --   25 --                                              prior art                                                                             0    --    --   --   15 60                                              E      0    --    --   --   45 60                                              prior art                                                                             10   --     40   0   0  30                                              A      50   --     50  20   0  45                                              prior art                                                                            --    --    --   --   80 90                                              C     --    --    --   --  100 100                                 __________________________________________________________________________      0 = no damage                                                                  100 = plants completely destroyed                                        

                  TABLE 10                                                         ______________________________________                                         Herbicidal action in strawberries;                                             postemergence treatment in the greenhouse                                              Test plants and % damage                                               Com-                   Lamium Mercuri-                                                                              Sola- Stel-                               pound         Fragaria amplexi-                                                                              alis   num   laria                               no.   kg/ha   vesca    caule  annua  nigrum                                                                               medie                               ______________________________________                                         30    2,0     20       100    100    100   100                                 14    1,0     0        100     98    100   100                                 82    0,5     0        30     100    100   100                                 144   1,0     20       60     100    --    100                                 123   1,0     10       60     100    100   100                                 113   1,0     20       100    100    --    100                                 194   1,0     0        100    100    100   100                                 ______________________________________                                          0 = no damage                                                                  100 = plants completely destroyed                                        

                                      TABLE 11                                     __________________________________________________________________________     Herbicidal action in peanuts and cotton;                                       postemergence application in the greenhouse                                            Test plants and % damage                                               Com-                                         Ipo-                              pound   Arachis                                                                             Gossypium                                                                            Alopocurus                                                                            Amaranthum                                                                           Chenopodium                                                                           Echinochloa                                                                          moea                                                                              Portulaca                                                                           Senbania                                                                            Solanum              no. kg/ha                                                                              hypognea                                                                            hirsutum                                                                             myosuroidoa                                                                           rotroflexus                                                                          album  crus galli                                                                           spp.                                                                              oleracea                                                                            exaltata                                                                            nigrum               __________________________________________________________________________     67  1,0 10   0     90     100   100    60    100                                                                               100  100  100                  68  0,5 10   --    90     100   100    70    75 100   95  100                  69  0,5 10   0     95      50   100    40    75 100   60  100                  70  1,0 0    0     95      50    90    --    60 100   60  100                  198 1,0 20   20    95      50   100    95    90 100  100  100                  77  2,0 0    10    95     --     90    100   60 100   95  100                  21  1,0 0    0     60     --    100    --    100                                                                               --   --   --                   165 0,5 15   0     85     100   100    --    -- 100  --   40                   106 0,5 10   15    90     100    0     --    --  70  --   --                   153 2,0 0    20    --     100   100    40    -- 100  --   100                  154 0,5 5    20    80     100   100    70    80 100   95  100                  31  2,0 0    0     --     100    90    --    100                                                                               100   70  --                   160 1,0 0    0     95     100   100    100   -- 100  100  100                  80  1,0 5    5     --     --    --     100   50 100  100  --                   161 0,5 15   0     100    --    100    90    -- 100  100  100                  __________________________________________________________________________      0 = no damage                                                                  100 = plants completely destroyed                                        

                  TABLE 12                                                         ______________________________________                                         Herbicidal action on weeds; postemergence application                          in the greenhouse                                                                      Test plants and % damage                                                                                         Xan-                                 Com-                    Ipo-              thium                                pound kg/    Alopecurus moea Sesbania                                                                              Sida  pensyl-                              no.   ha     myosuroides                                                                               spp. exaltata                                                                              spinosa                                                                              vanieum                              ______________________________________                                         29    1.0    95         83   100    100   100                                        2.0    100        88   100    100   100                                  161   2.0    100        85   100    100   60                                   82    2.0    98         82   100     60   100                                  162   1.0    94         65    90    --    90                                         2.0    98         65   100    --    90                                   89    1.0    90         100  80      60   40                                         2.0    95         100  100    100   90                                   164   2.0    95         90   100    --    80                                   105   2.0    95         --   100     90   80                                   68    2.0    94         93    98    100   50                                   71    2.0    95         100  100    100   --                                   106   2.0    95         90    80     80   --                                   165   2.0    95         100  100    100   --                                   144   1.0    50         95   100    100   100                                        2.0    80         95   100    100   100                                  149   1.0    70         90   100    100   40                                         2.0    80         100  100    100   100                                  ______________________________________                                          0 = no damage                                                                  100 = plants completely destroyed                                        

                                      TABLE 13                                     __________________________________________________________________________     Selective herbicidal action; postemergence application in the greenhouse       Com-    Test plants and % damage                                               pound   Triticum                                                                            Zea                                                                               Amaranthus                                                                           Chenopodium                                                                           Euphorbia                                                                            Martricaria                                                                          Sinapis                                                                            Sesbania                                                                            Solanum                      no. kg/ha                                                                              aestivum                                                                            mays                                                                              retroflexus                                                                          album  geniculata                                                                           spp.  alba                                                                               exaltata                                                                            nigrum                       __________________________________________________________________________     202 0.5 5     5 100   100    100   100   100 100  100                              1.0 10   12 100   100    100   100   100 100  100                          151 0.5 0    -- --    100    100   100   100  90  100                              1.0 0    -- --    100    100   100   100 100  100                          __________________________________________________________________________

EXAMPLE 11

9 parts by weight of compound 1 is mixed with 1 parts by weight of N-methyl-α-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 12

20 parts by weight of compound 2 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 13

20 parts by weight of compound 3 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 14

20 parts by weight of compound 1 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 15

20 parts by weight of compound 2 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.

EXAMPLE 16

3 parts by weight of compound 3 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

EXAMPLE 17

30 parts by weight of compound 4 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

EXAMPLE 18

40 parts by weight of compound 1 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.04 wt% of active ingredient.

EXAMPLE 19

20 parts of compound 2 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained. 

We claim:
 1. A pyrazole of the formula ##STR169## where R¹ is hydrogen,R² is hydrogen, R³ is phenyl, R⁴ is methoxycarbonyl, and R⁵ is hydrogen or methyl, and the agriculturally acceptable acid addition salts thereof.
 2. A pyrazole of the formula ##STR170## wherein R¹ is hydrogen, R² is hydrogen, R³ is phenyl, R⁴ is methoxycarbonyl, and R⁵ is methyl. 